Using peptide coupling methods can you speculate on the need for a scavenger amine? Also, what makes a good coupling agent for our target substrate? I see that many are available.. Any recommendations on others? I remember reading one comes with an accompanying color change to indicate completion.
overunity33
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jon
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so your saying convert it to 2-bromolysergic acid first?
i was under the impression temperatures of 200 C under high vacum were nessecary to remove the water of crystallization from the piperidine nitrogen of the ergoline nucleus.
and clorinated intermediates forming in what position of the molecule? i don't see chlorine adding just from contact with zinc chloride.
zinc chloride may catylize the chlorination but in this case the cl- ion has a proton for a counterion and the acid is buffered by the ammonium ion so, i'm just not understanding your logic.
take some time and give that paper a more thorough review and consideration.
i think grignard reagents formed from that molecule would'nt work. i could be wrong expiriment always trumps theory any day of the week.
i mean if you have lab notes saying you dried lysergic acid under those conditions that's great!
but everything else i read says high vacum and lots of heat which could lower your yeilds due to decomp.
and you said
*stray zinc in the rxn could take up the bromine but something would have to donate a carbon otherwise the whole molecule is going to fall apart. if you started with lysergic acid instead of bromocriptine i could see it working.*
that would leave a carbocation but what really happens is bromine is'nt "taken up" it's transmettalated to an organo zinc bromide similar to a grignard reagant except it's zinc. then, ammonium chloride comes along and "quenches that" if you will making a mixed zinc salt and the c-h bond.
i was under the impression temperatures of 200 C under high vacum were nessecary to remove the water of crystallization from the piperidine nitrogen of the ergoline nucleus.
and clorinated intermediates forming in what position of the molecule? i don't see chlorine adding just from contact with zinc chloride.
zinc chloride may catylize the chlorination but in this case the cl- ion has a proton for a counterion and the acid is buffered by the ammonium ion so, i'm just not understanding your logic.
take some time and give that paper a more thorough review and consideration.
i think grignard reagents formed from that molecule would'nt work. i could be wrong expiriment always trumps theory any day of the week.
i mean if you have lab notes saying you dried lysergic acid under those conditions that's great!
but everything else i read says high vacum and lots of heat which could lower your yeilds due to decomp.
and you said
*stray zinc in the rxn could take up the bromine but something would have to donate a carbon otherwise the whole molecule is going to fall apart. if you started with lysergic acid instead of bromocriptine i could see it working.*
that would leave a carbocation but what really happens is bromine is'nt "taken up" it's transmettalated to an organo zinc bromide similar to a grignard reagant except it's zinc. then, ammonium chloride comes along and "quenches that" if you will making a mixed zinc salt and the c-h bond.
jon
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a scavanger amine just sucks up protons formed during the coupling or more succinctly acidic protons.
in that case you would get some kind of phosphonic acid.
i reckon he preferred this asymmetrical amine because of steric reasons if you look at that pentavalent bulky orgaonophosphorus compound.
in that case you would get some kind of phosphonic acid.
i reckon he preferred this asymmetrical amine because of steric reasons if you look at that pentavalent bulky orgaonophosphorus compound.
Vesp
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IasaF13 or TcorF01 are some of the fungi that infect the Convolvulaceae plants, which include Turbina corymbosa, Argyreia nervosa, and Ipomoea violacea.
and additionally, this was shown to me earlier...
Analysis of Blue Cheese for Roquefortine and Other Alkaloids from Penicillium roqueforti
Peter M. Scott* and Barry P.C. Kennedy
J. Agric. Food Chem., 1976, 24 (4), pp 865-868
DOI: 10.1021/jf60206a028

hxxp://pubs.acs.org/doi/abs/10.1021/jf60206a028
Isolation of Festuclavine and Three New Indole Alkaloids, Roquefortine A, B and C from the Cultures of Penicillium roqueforti
Sadahiro OHMOMO1), Takao SATO1), TEIICHI UTAGAWA1) and Matazo ABE1)
Laboratory of Industrial Microbiology, Faculty of Agriculture, Tokyo University of Education
hxxp://www.journalarchive.jst.go.jp/english/jnlabstract_en.php?cdjournal=bbb1961&cdvol=39&noissue=6&startpage=1333
Genetics of Ergoline Alkaloid Formation in Penicillium roquefortii
SOOBOK L. HONG AND JAMES E. ROBBERS*
Department of Medicinal Chemistry and Pharmacognosy, School of Pharmacy and Pharmacal Sciences, Purdue
University, West Lafayette, Indiana 47907
Received 25 October 1984/Accepted 4 February 1985
hxxp://www.ncbi.nlm.nih.gov/pmc/articles/PMC238668/pdf/aem00144-0014.pdf
and additionally, this was shown to me earlier...
Analysis of Blue Cheese for Roquefortine and Other Alkaloids from Penicillium roqueforti
Peter M. Scott* and Barry P.C. Kennedy
J. Agric. Food Chem., 1976, 24 (4), pp 865-868
DOI: 10.1021/jf60206a028
Quote
Compounds isolated from P.roqueforti culture media include "PR toxin", a sesquiterpenoid metabolite (Wei et al., 1973, 1975), and three incompletely characterized substances of unknown structure designated toxins-1, -2, and -3 (Kanota, 1970). The ability of P.roqueforti to produce alkaloids was shown by Taber and Vining (1958), Abe et al (1967), and Bekmakhanova (1974). Only recently, however, have crystalline alkaloids been isolated and characterized. Ohmomo et al (1975) isolated the known compound festuclavine and two other clavine alkaloids named roquefortine A (the major alkaloid) and roquefortine B, for which the unusual structures 7-acetoxy-6,9-dimethylergoline and 6,9-dimethylergolin-7-ol, respectively, were proposed. A fourth alkaloid, roquefortine C, was not structurally characterized. Scott et al. (1976) obtained two alkaloids from the mycelium of a strain of P. roqueforti used in cheese processing. The major alkaloid, designated roquefortine, was assigned the structure 10b-(1,1-dimethyl-2-propenyl)-3-(imidazol-4-ylmethylene)-5a,10b,11,11a-tetrahydro-2H-pyrazino-[1',2':1,5]pyrrolo[2,3-b]indole-1,4-(3H,6H)-dione and had physical properties similar to those published for roquefortine C. The minor alkaloid, isofumigaclavine A (8-acetoxy-6,8-dimethylergoline), was a stereoisomer of fumigaclavine A (Spilsbury and Wilkinson, 1961). Most of the physical properties reported for roquefortine A are similar to those of isofumigaclavine A, and they may in fact be the same compound. However, isofumigaclavine B (6,8-dimethylergoline-9-ol), obtained by hydrolysis of isofumigaclavine A, had a higher melting point than that reported for roquefortine B.

hxxp://pubs.acs.org/doi/abs/10.1021/jf60206a028
Isolation of Festuclavine and Three New Indole Alkaloids, Roquefortine A, B and C from the Cultures of Penicillium roqueforti
Sadahiro OHMOMO1), Takao SATO1), TEIICHI UTAGAWA1) and Matazo ABE1)
Laboratory of Industrial Microbiology, Faculty of Agriculture, Tokyo University of Education
hxxp://www.journalarchive.jst.go.jp/english/jnlabstract_en.php?cdjournal=bbb1961&cdvol=39&noissue=6&startpage=1333
Genetics of Ergoline Alkaloid Formation in Penicillium roquefortii
SOOBOK L. HONG AND JAMES E. ROBBERS*
Department of Medicinal Chemistry and Pharmacognosy, School of Pharmacy and Pharmacal Sciences, Purdue
University, West Lafayette, Indiana 47907
Received 25 October 1984/Accepted 4 February 1985
hxxp://www.ncbi.nlm.nih.gov/pmc/articles/PMC238668/pdf/aem00144-0014.pdf
